ES2425471A1 - Concentrated polymer composition ("masterbatch"), production method thereof and use of same for adding to polyester fibres and filaments - Google Patents

Abstract

The invention pertains to the field of synthetic-fibre production for the textile industry and relates to the design and use of a concentrated polymeric composition ("masterbatch") comprising: a polymer from the metlacrylate family as a support polymer, representing between 30 wt.-% and 99 wt.-% of the polymer composition and at least one additive and/or pigment representing between 1 wt.-% and 70 wt.-% of said composition. During the extrusion process, the composition of the invention is incorporated into the molten fibre- and filament-forming polyester polymers in order to increase speed in the spinning process (productivity).

Description

quot; CONCENTRATED POLYMER COMPOSITION (quot; MASTERBATCHquot;), ITS MANUFACTURING PROCEDURE, AND ITS USE FOR THE ADDITIVATION OF POLYESTER FILES FIBERS AND FILMS; Object of the invention:

The invention pertains to the field of the production of synthetic fibers, mainly for the textile industry, and in particular to the manufacture of synthetic threads and fibers of polyester polymers by the melt spinning process.

Specifically, the invention relates to the design and use of a concentrated polymer composition.

(quot; masterbatchquot;), for incorporation during the extrusion process to the melts of polyester polymers forming fibers and filaments, whose purpose is to achieve speed improvement in the spinning process (productivity).

Specifically, the polymer composition of the present invention will preferably be applied to pre-oriented threads in order to be able to spin them at higher

speeds

but with a behavior rheological (curve

load-elongation)

Similary to when be hilan to Minor

speed without

quot; masterbatchquot; Incorporated.

State of the art:

A support polymer or also called in the technical sector as quot; carrierquot; it is the medium in which a concentrate of color pigments or other additives is dispersed, the assembly being known as `` masterbatchquot ;, which is dosed to the main polymer to modify

the properties of the fibers and filaments, resulting in products with a technical differential value and specific improvements for the applications to which they are intended.

There is a great variety of "masterbatchquot" on the market; whose composition depends on the purposes for which they are used; however, the use of polymethylmethacrylate (PMMA) as a carrier or carrier of additives in a "masterbatch" is not known to date, in order to increase productivity in the melt spinning process.

In melt spinning processes, PMMA has been used as an additive that reduces orientation, such is the case of Spanish patent no. ES2210929, in which polyester fibers and filaments containing PMMA added in amounts between 0.1 and 4% by weight in relation to the polymer forming the yarns are disclosed. The PMMA is injected into the main melt stream of polyester, dispersed and homogenized in the molten polymer, with the result of being able to increase the elongation at breakage (elongation) at high spinning speeds.

For the same purpose it is used in US patents no. US2004076823 and Japanese no. JP11350277. US2004076823 refers to a coextruded composition of PTT polyester (polymethyl terephthalate) fibers with the addition of a PMMA resin, among others, achieving an increase in elongation at break

from

the fiber  from a 30% the that It allows increase the

speed

from spinning In the patent JP11350277 be

disclose

he effect of the PMMA how limiter from the

orientation

crystalline to the be used how additive in

a composition of polyester threads or filaments,

managing to increase the elongation at breakage of

fiber with a view to thread preparation

bulky (HB) by mixing threads with different

shrinkage capacity (differential shrinkage).

5

The need of the industry is well known

achieve productivity improvements without prejudice to

The quality of manufactured products. In the case of

fiber manufacturing for the textile industry this

Need is especially pressing. The present

10

invention provides a solution to this problem by

using a quot; masterbatchquot ;.

It is known that the incorporation of a "masterbatchquot;

specific can significantly influence the color,

performance and costs in spinning processes. From his

fifteen

correct choice and design will depend on the effectiveness of

an additive and its compatibility with the polymer

fiber component.

Therefore, the preparation of a

quot; masterbatchquot; with a support polymer with which

2 o

I managed to disperse important concentrations of a ditive

without changing its characteristics during and

after its dispersion and that allows to increase the productivity during the spinning of the fibers and

polyester filaments 25

Description of the invention:

The main objective of the present invention is the formulation and use of a polymer composition ("masterbatch") comprising a polymer of the family 30 of methacrylates as a support polymer ("carrier" of pigments and / or additives dispersed in the same, for incorporation during the extrusion process to the

fades

from polymers from polyester trainers from fibers,

whose

purpose is get the improvement from the

productivity

in the process of spinning

This

objective be achieves Thank you to the optimal

qualities

that brings he polymer from the family from the

methacrylates when used as a carrier in the

quot; masterbatchquot ;, in which at least one pigment and / or an additive is dispersed.

Preferably, the member of said family used as carrier polymer quot; carrierquot; in the quot; masterbatchquot; It is polymethylmethacrylate (PMMA).

Said polymethylmethacrylate polymer, used as a support polymer in the "masterbatchquot", and the results obtained when using it, will be used hereafter to adequately explain the present invention.

However, this explanation should not be construed as limiting the use of PMMA as a support polymer, since similar results have been obtained by using other polymers that are part of the methacrylate family as an alternative to PMMA.

Therefore, from now on, PMMA will be used as a support polymer, it being understood that any reference to this polymer may be extended to other members of the methacrylate family.

Advantageously, the use of a quot; masterbatchquot; with PMMA as carrier it does not cause the polymer in which the processing problems are dosed by degradation of this polymer during the mixing that is carried out in the extruder.

PMMA is an inert material that is not compatible (miscible) with thermoplastic forming polymers

of fibers. It is an amorphous plastic, and its influence on these polymers is limited only to its rheological behavior, without producing any structural modification, so it is suitable for use as a carrier; in a quot; masterbatchquot ;.

Sometimes this support polymer may be composed of mixtures of PMMA with one or a combination of at least two of the following polymers: polybutyleneterephthalate (PBT), polyethylene terephthalate

(PET), polymethyl terephthalate (PTT), or polylactic acid (PLA), in order to optimize the final properties of the "masterbatchquot ;.

As already mentioned, the polymer composition of the invention is added or added during the extrusion process to the melts of fiber-forming polyester polymers. The denomination quot; polyesterquot; It groups all the members of a family of polymers whose chain is formed by monomers linked by ester functions, such as polyethylene terephthalate (PET), polybutyleneterephthalate (PBT), polytrimethylene terephthalate

(PTT), or polylactic acid (PLA).

After successive investigations and tests, it has been defined that in order to achieve the desired ends in the improvement of productivity in the spinning process, the composition of the masterbatchquot; referred to in the present invention will preferably comprise polymethylmethacrylate (PMMA) with a molecular weight between 10,000 and 500,000 g / mol, and will be contained in an amount between 30% and 99% by weight of said concentrated polymer composition or quot; masterbatchquot ;.

Likewise, it has been determined that the final concentration of PMMA in the fiber-forming polymer to be extruded preferably reaches up to 10% by weight in the final mixture or, what is the same, in the melting of said polymer, whereby very important increases in the productivity of the spinning process.

In addition to PMMA, the polymer composition of the present invention contains between 1% and 70% by weight of pigments and / or additives and optionally other polymers and dispersing agents. The percentage of

pigments and / or additives is a function, among other things, of the type and characteristics of said pigments and

additives, and of the polymers that will be additive.

The pigments used in the quot; masterbatchquot; they will be chosen from an organic pigment, an inorganic pigment, or a mixture of them.

Preferably the pigments used in the polymer composition "masterbatchquot; of the present invention will be Smoke Black, or titanium dioxide (Ti02). In this sense, it is described in the present invention the existence of a surprising and unexpected synergistic effect, derived from the combination of PMMA with each of these pigments, said combination enhances the orientation decrease allowing an increase in productivity without having to reach high dosage levels in excess.

On the other hand, the additives used for the preparation of the polymer composition are chosen from: lubricants, antistatic agents, plasticizers,

stabilizers,

antioxidants, compatibilizers and

flame retardants

So how blends or combinations from these

   products.

In the case where the support polymer can be composed of mixtures of PMMA with other polymers, such as PBT, PET, PTT and PLA, in order to optimize the final properties of the "masterbatch"; said polymers will be contained in a amount between 50% and 70% by weight of the polymer composition.

The presence of dispersing agents is linked to the manufacturing process. As described in this invention, a pre-mixing phase of polymers and pigments and / or additives is sometimes necessary in the presence of dispersing agents in order to achieve adequate dispersion of the pigments and additives in the subsequent extrusion phase. .

The concentrated polymer composition of the present invention will be dosed during the extrusion process of the melts of polyester polymers forming

fibers

The

influence to level rheological from the addition

(additivation)

from the composition polymeric in saying

molten,

be concrete in a decrease of the grade from

orientation of the additive polymer, decrease that will depend on the dosage applied.

The spinning system used to obtain the thread or fiber, from the melts added with the quot; masterbatchquot; of the present invention, it will be fusion spinning since it is synthetic fibers and thermoplastic polymers, especially polyester polymers.

Spun yarns or fibers are generally of the family of pre-oriented threads (POY), which are mainly used in the manufacture of textured threads.

The polymeric composition of the present invention can be applied in the manufacture of these pre-oriented threads (POY) in order to be able to spin them at higher speeds but with a rheological behavior

(load-elongation curve) similar to when spinning at lower speed without quot; masterbatchquot; Incorporated.

The preoriented threads are threads that are collected at speeds that can range between 500 and 4500 m / min. These threads have a biphasic fine structure (microstructure) with an amorphous phase oriented

or mesomorph embedded or integrated in a matrix

disoriented,

Y with a absence almost total from zones

crystalline

when the speed from spinning no is

higher

to 3500 m / min

The orientation of the POY threads is completed in their subsequent processing, as is the case with the texture. The manufacture of POY threads allows an increase of the productivity of the order of 30%, as well as an excellent processing in the operation of texture. POY threads have a toughness of the order of 18 CN / tex and an elongation at break around 150%. The load-elongation curve of the POY wires has an initial stretch of elastic behavior globally (zone of the initial module), which is followed by a large creep zone (increased elongation with hardly any increase in load), to this creep zone It follows a reinforcement zone, with a linear section, until breakage occurs. An interesting parameter of the load-elongation curve of the POY threads refers to the load or effort corresponding to 100% elongation. The point corresponding to these coordinates is usually located in the reinforcement zone. This burden that

causes an elongation of 100% can be considered as a global parameter of orientation (orientation index, 1100) • The lower its value, the less oriented the fine structure of the wire will be and the greater its deformability (ductility / stretchability) and lower its stiffness . In this context it will be known as orientation index or hoo.

When the spinning speed is increased, the elongation at breakage of the POY threads decreases and increases

he

hoo. The speed from spinning from the threads POY

destined

to its later texture comes limited by

he

done from that these must present a determined

elongation

to the break, O well of the effort or load

that

there is  that Apply for produce a elongation of the

100%

(h00) in the thread POY

If, by adding the melt of the polymer to be extruded, the elongation at breakage of a POY wire can be increased, it will happen that a decrease of 1100 will also take place. This will mean that the spinning speed can be increased to the extent that the 1100 does not exceed the one corresponding to the spinning speed when it is a non-additive polymer melt.

The results obtained with the application of the polymer composition of the invention clearly demonstrate its effectiveness in overcoming the technical problem posed in relation to the increase in the spinning process performance.

With the dosage of a polymeric composition quot; masterbatchquot; having as carrier polymer quot; carrierquot; PMMA and a pigment and / or additive such as those described above, results are obtained that demonstrate that the tensile or deformation qualities that are contributed to these fibers are superior to those of a "masterbatchquot; containing another type of carrier with the same pigment or additive, as well as a stretchability

(ductility) superior to the one that it possesses in equal conditions of extrusion.

Regardless of the fact that it is more regular in the extrusion process during spinning, the threads obtained by applying a "masterbatchquot; With PMMA as a support polymer and additives and / or pigments such as those described here, they have a fine structure with a lower degree of orientation that allows to increase the speed of thread collection, which results in a very high productivity (spinning speed) superior to when other polymers are used as carrier. In this regard, the results show that increases in spinning speed greater than 20% are obtained.

The effectiveness of additivation with the composition

polymeric

quot; masterbatchquot; from the Present invention be

confirm

by he done from that to the increase the

concentration

from polymethylmethacrylate (PMMA) in he

melting of the fiber-forming polymer that is manufactured also increases the effects obtained, keeping the spinning speed constant.

In one of the possible embodiments of the invention the concentrated polymer composition comprises between 30-50% by weight of polymethylmethacrylate (PMMA) as a support polymer, between 50-70% by weight of PBT, and between 1-5% in weight of additive and / or pigment.

Said polymer composition is added in an amount between 4% and 8% by weight of the fiber and filament forming polymer, and the

Polymethylmethacrylate is contained in an amount between 1.6% and 3.2% by weight in said polymer.

The application of a composition such as that described decreases the orientation index of pre-oriented polyester threads POY 290/48 dtex to values between

15.4 (CN / tex) and 11.8 (CN / tex) when spun at speeds between 2000 and 4500m / min.

It is a preferred embodiment of the invention a concentrated polymer composition comprising between 60-90% by weight of polymethylmethacrylate (PMMA) as a support polymer, and at least one additive and / or a pigment being contained in an amount between 10% and 40% by weight of said polymer composition.

It is yet another preferred embodiment of the invention a concentrated polymer composition preferably comprising between 60-80% by weight of polymethylmethacrylate (PMMA) as a support polymer and between 20-40% by weight of Smoke Black as a pigment.

This concentrated polymer composition is added in the extrusion process to the melts of polyester polymers forming fibers and filaments, in an amount between 2% and 8% by weight, so that the polymethylmethacrylate is contained in an amount between l. 4% and 5.6% by weight in said melt of the fiber and filament forming polymer.

This second preferred composition decreases the orientation index of pre-oriented polyester threads POY 290 dtex to values between 11.7 (CN / tex) and

8.1 (CN / tex) when they are spun at speeds between 2000 and 4500 m / min., And increases their elongation at breakage to values between 152% and 186%.

The formulation of the "masterbatchquot; This allows the two main components to be combined and concentrated to the maximum, that is, pigment and PMMA, making it possible to obtain a final product that provides the best desired functionality at a perfectly viable dosage percentage.

The known alternative to obtain the same functionality would be to add 2 different masterbatch: one to increase productivity and the other to modify the color. In this case the total cost of the two masterbatch would be much higher and the total dosage level would be so high that it would affect both the processability and the final properties of the thread.

POY threads added with this quot; masterbatchquot; they were subsequently textured allowing the obtaining of textured threads that presented an increase in the elongation values at break between 15% and 35%, thereby increasing the productivity in their spinning to values of up to 22.3% in relation to the yarn textured polyester without additive.

Another preferred embodiment of the invention is a concentrated polymer composition comprising between 50-95% by weight of polymethylmethacrylate (PMMA) as a support polymer and between 5-50% by weight of Titanium Dioxide (Ti02) as a pigment.

Said polymer composition is added to the melt.

from

saying polymer  from polyester in a quantity between he

2%

Y he 8% in weight of the molten, Y he

polymethylmethacrylate

is content in a quantity

   between

he 1.7% Y he 6.8% in weight in he molten.

This third composition allows the orientation index of pre-oriented polyester yarns POY to be reduced to values between 12.1 (CN / tex) and 7.9

(CN / tex),

Y a increase in elongation to the break to

values

between 152% Y 185%, when They are yarn to

speeds

between 2000-4500 m / min

The

threads POY additive with East quot; masterbatchquot; be

textured

later, allowing the obtaining from

threads

textured bent with a elongation to the

Breaking between 22% and 37.2%, thereby increasing productivity by up to 22.3% in relation to textured polyester yarn without additive.

Manufacturing procedure of the "masterbatchquot ;:

Another object of the present invention is the manufacturing process of a "masterbatch" as defined in this invention, which comprises an extrusion phase and optionally a pre-mixing pre-phase.

Sometimes this first pre-mixing phase is not necessary for some polymers, pigments and additives, and can be dosed directly in the extrusion phase. Pre-mix phase:

This first phase takes place in equipment called turbo-mixers or the like where the pigments and / or additives are pre-dispersed by using one or more dispersing agents, compatible with the base polymer and with the polymer component of the fiber to be manufactured In order for the pre-dispersion to be optimal, the agglomerates must be broken up by means of the mechanical stress provided by the turbo-mixer blades and the subsequent imbibition or impregnation of

Pigment particles Agglomerates are formed as a result of strong interactions between pigment particles. This phenomenon happens especially at high concentrations of organic pigment. Imbibition is understood as the phenomenon of covering the surface of a solid with a liquid: dispersing agents, such as waxes, melt at the temperatures reached within the turbo-mixer and cover the other components of the mixture.

Extrusion phase:

The main objective of this phase is to obtain a good dispersion (dispersive mixture) and homogenization (distributive mixture) of the components of the quot; masterbatchquot ;. There is a wide variety of extrusion equipment, the choice of which will depend on the characteristics and properties of the product to be extruded. The one used in the present invention to manufacture a "masterbatchquot; PMMA is a bi-spindle spindle extruder, which is characterized by the same direction of rotation of its spindles. These extrusion equipment transfer a large amount of mechanical energy, called shear force, to the material, which allows high content of pigments and / or additives to be dispersed. The configuration of the spindles is essential to ensure good productivity and optimum product quality. The spindles are formed by different

elements

assembled that in function from its geometry Y

position,

distribute, disperse, or transport he

material.

He treatment that suffers he material during

its

He passed by he team extruder It depends from the

Spindle configuration being equally important both the type of elements used and their position in the spindle. As an example, two configurations with the same elements but different distribution in the

spindle

will produce materials extruded from quality

different

(dispersion, distribution, performance

coloristic).

Others elements external that influence in

extrusion

They are the dispensers, bathtubs, systems from

dried and

the farmers (granulators).

Application procedure of quot; masterbatchquot ;:

Preferably the method of application of the polymeric composition quot; masterbatchquot; of the present invention is carried out according to the following procedure:

The starting point for fusion spinning is thermoplastic polymers in the form of chips or pellets. These melt inside the extruder forming a fluid viscous mass. The viscous mass is dosed by means of a volumetric pump to a filtration system and a hole plate called a row. The molten polymer is forced to pass through the holes in the row, applying high pressure values, obtaining a set of filaments, which together form the thread. The cooling of the viscous mass at the exit of the row is carried out by a controlled flow of air, the threads are subsequently lubricated with an emulsion oil emulsion and finally collected in a winder.

The addition of the polymer composition quot; masterbatchquot; of the present invention is carried out in the melt extrusion zone of the fiber forming polymer, it can be made solid by a gravimetric system or in a viscous form by means of a side extruder.

The temperature profile applied in the extruder in

The present development is between 290 and

300 ° C This profile can be modified based on

the dimensions of the extruder, the residence time

5

of the melt and other parameters that may

vary according to different extrusion equipment.

Description of the figures.

Figure 1 shows the evolution of the elongation at

10

the breakage and orientation index of the threads in

Dosing function of a 15% masterbatch

PMMA in PBT in the melt of the polymer to be extruded,

always at the same spinning speed (3000 m / min.).

Figure 2 shows the evolution of the index of

fifteen

orientation depending on the concentration of PMMA in the

molten polymer to extrude at different speeds

spinning

Figure 3 shows the stretching ratio in the

texture (residual stretch) depending on the index of

2 o

guidance for different elongations at break

of the textured thread.

Figure 4 shows the evolution of the index of

orientation at two different spinning speeds, in

function of the concentration of PMMA in the melt of

25

polymer to extrude. In this case the "masterbatchquot; is a

combination of PMMA and PBT.

Figure 5 shows the evolution of the index of

orientation at two different spinning speeds, in

function of the concentration of PMMA used in the

30

molten polymer to extrude with carbon black as

additive.

Figure 6 shows the load / elongation curves of

   a thread collected at a speed of 3500m / min.

using as a black smoke additive, with or without the use of PMMA as a carrier.

Figure 7 shows the 1-load loading curves obtained by applying the same concentrations of PMMA in two different formulations of the polymer composition, or masterbatch, as well as the base polymer.

(PET RT-20).

Figure 8 shows the load / elongation curves when a "masterbatchquot" is used; PMMA 1 Ti02 at different dosages.

Figure 9 shows the evolution of the elongation at break and the orientation index as a function of the concentration (%) of PMMA in the polyester melt.

Figure 10 shows the load / elongation curves of the textured threads obtained when a "masterbatchquot" is used; PMMA / Ti02 at different dosages.

Figure 11 shows the evolution of the elongation at break as a function of the concentration (%) of PMMA in the polyester melt when a "masterbatchquot" is used; PMMA 1 Ti02 at different dosages.

Figure 12 shows the load / elongation curves of the preoriented threads resulting from the addition of a "masterbatch"; PMMA / carbon black at two different dosages.

Description of an embodiment of the invention:

In accordance with the present invention a concentrated polymer composition (also referred to in the art as "masterbatch") for the additivation of fibers and / or filaments of thermoplastic polymers during the extrusion process is formed by: (a) a polymethylmethacrylate (PMMA) with a molecular weight of

100,000 g / mol as carrier polymer, carrierquot ;, and (b) an additive and / or a pigment.

The polymeric composition of the present invention covers a range of PMMA / additive and pigment compositions between 30/70% and 99/1%, obtaining very satisfactory results, since it allows to decrease the orientation index and increase the elongation at break , and thereby achieve increased spinning speed.

The final concentration of PMMA in the fiber-forming polymer to be extruded can reach up to 10% by weight of the final mixture (i.e. "masterbatch" with the fibers and / or filaments of thermoplastic polymers), allowing this concentration range to reach The desired results.

The results referred to above are shown in Figure 1, in which it can be clearly seen how, for the same spinning speed, the orientation index decreases as the concentration of PMMA increases, acting as carrier or support in the composition polymeric quot; masterbatchquot ;. This results in less oriented (more deformable) threads, which may allow working at higher spinning speeds and, at the same time, achieve elongation at breakage of non-additive threads.

The elongation at break, contrary to what happens with the orientation index, evolves so that, as can be seen in Figure 1, as the concentration of PMMA in the polymer increases the elongation at break also increases, which it allows the spinning speed to be increased with the consequent increase in productivity.

Figure 2 refers to the evolution of the orientation index as a function of the concentration of PMMA in the melt for different spinning speeds. In it it can be seen that the addition of 3.2% PMMA to the melt when spun at 3490 m / min. leads to threads with the same orientation index (I 100) as when spinning at 3000 m / min. in the absence of PMMA, with the consequent increase in productivity.

Figure 3 shows the residual stretch ratio (stretched in the texturing operation) as a function of the orientation index (I 100) of the POY thread for textured threads with different elongations at breakage. It shows that, for a given elongation at the breakage of the textured thread, the smaller the I 100, the greater the drawing ratio that can be applied in the texturing machine. On the other hand, it also happens that, for a given value of 1100, the greater the elongation at breakage of the textured yarn, the lower the residual stretch ratio. This is logical since the greater the elongation at breakage of the textured thread, the smaller the orientation (residual stretched ratio) that is applied in the texture maker will have to be.

Examples of realization:

Example 1:

The results of the tests presented in Table 1 and represented in Figure 4 were obtained by adding a polymer composition ("masterbatch" in the form of pellets or chips) in the extrusion process according to a gravimetric addition procedure. . The "masterbatchquot; it contained a

40% PMMA and 60% by weight of PBT. Once the quot; masterbatchquot; it melted and mixed with the molten polymer in the extruder at a temperature between 290 ° C and 300 ° C forming a fluid viscous mass that, forced to

5 passing through the holes in the row by application of high pressures, is transformed into the set of filaments that collected at 3500 m / min. they form a POY thread of title 290/48 dtex.

Table 1 contains the values of the index of

10 orientation (I 100) when spinning at 3000 and at 3500 m / min. depending on the percentage of PMMA added to the polymer to be extruded. Its examination allows to indicate that with an incorporation of 3.2% of PMMA (8% of the quot; masterbatchquot; indicated) the same value of I 100 is spinning at

15 speed of 3500 m / min. that when it spins at 3000 m / min. in the absence of PMMA.

Table no.1

Masterbatch dosage (%)

PMMA concentration (%) Orientation index (CN / Tex) 3000 3500 m / min. m / min

or

or

11.7 19.4

4

1.6 9.7 15.9

6

2.4 8.7 13.4

8

3.2 7.7 11 '8

Example 2: The results of the tests presented in Table 2 were obtained by adding, in the extrusion process of a polyester melt, a polymeric composition

quot; masterbatchquot; in the form of pellets or chips according to a gravimetric method of addition. The polymer composition contained 70% by weight of PMMA and 30% by weight of carbon black as an additive. The procedure

5 used for the addition and obtaining of the yarn or fiber was the same as described in example 1, finally obtaining a POY 290/48 dtex polyester yarn.

Table 2 shows the value of the orientation index (I100) when spinning at 3000 and at 3500 m / min. in function 10 of the percentage of PMMA incorporated into the melt starting from the masterbatchquot; indicated. It can be seen that the presence of 2.1% of PMMA spinning at 3500 m / min. it leads to an I 100 equal to that which results from spinning at 3000 m / min. in the absence of PMMA. The values in Table 2

15 are graphically represented in Figure 5.

Table no.2

Masterbatch dosage (%)

PMMA concentration (%) Orientation index (CN / Tex) 3000 3500 m / min. m / min

or

or

11.5 18.4

3

2.1 8.6 11.6

4

2.8 7.9 10.7

5

3.5 7, 1 8.3

Analyzing together examples 1 and 2,

20 clearly appreciates a synergistic effect resulting from the combined use of PMMA with pigment (carbon black) in the same quot; masterbatchquot ;. Comparing the tables it is observed that the PMMA content necessary to preserve the

Orientation index of the original yarn, without additive and spinning at 3000m / min., goes from 3.2% to 2.1% in the event that the 11masterbatch11 also incorporates carbon black.

It is the formulation of this 11masterbatch11 that allows the two main components to be reconciled and concentrated to the maximum, that is, pigment and PMMA, making it possible to obtain a final product that provides all the desired functionality at a perfectly viable dosage percentage.

The known alternative to obtain the same functionality would be to add 2 different masterbatch: one to increase productivity and the other to modify the color. In this case the total cost of the two masterbatch would be much higher and the level

from

dosage global could reach easily he 8 or

10%

These levels from dosage in general no They are

viable

already that reduce in excess he percentage from

polymer

base hurting the processability Y the

properties

late.

Example 3:

The results that are represented in Table 3 and Figure 6 correspond to tests carried out to determine the effects of PMMA on increasing the stretchability of a 290/48 dtex POY polyester thread using carbon black as a pigment and PBT as carrier in one case, and PMMA in another. The speed of

spinning remained constant at 3500 m / min., as well as the other conditions of the extrusion and spinning process.

Both quot; masterbatchquot; they contained a weight ratio of 70% support polymer (PMMA or PBT) and 30% carbon black, and were dosed at 4% relative to the molten polymer to be extruded.

5 Curves 1-3 in Figure 6 correspond to the quot; masterbatchquot; which contained a weight ratio of 70% PBT 1 30% carbon black, and curves 4-6 correspond to the quot; masterbatchquot; with a weight content of 70% PMMA 1 30% carbon black.

10 In Table 3 it can be seen that the presence of PMMA leads to wires with a significantly greater elongation at break and a much lower orientation index than when PBT is used as a support for the black smoke pigment. This shows the

15 much greater efficiency of PMMA to decrease the orientation of polyester POY threads.

Table no.3

Masterbatch composition

Tenacity (CN / Tex) Elongation at break (%) Orientation Index (CN / Tex)

70% PBT 1 30% Smoke Black

20.0 127.7 15.5

70% PMMA / 30% Smoke Black

17.1 166.3 9.1

Example 4:

20 POY polyester threads of 210/48 dtex were prepared with a spinning speed of 3500 m / min., One without additivation, another additive with a "masterbatchquot"; with a weight content of 85% PMMA 1 15% Ti02, and another with a quot; masterbatchquot; with a content in

25 weight of 70% PMMA 1 30% Smoke Black. The additive threads contained in both cases 2, 8% by weight of

PMMA with respect to the fiber forming polymer. Another thread was added with Smoke Black PBT 1 with a weight content of 70% Smoke PBT 1 30%. The spinning process conditions were the same as those of the spinning process.

5 example l.

From the values in Table 4 it can be deduced that the use of PMMA as a support for the quot; masterbatchquot; it leads to the highest values of elongation at breakage and the lowest orientation rates. Also appreciated

10 that the presence of Smoke Black in a "masterbatchquot; It produces a certain effect on traction parameters.

Table no.4

Test

Masterbatch composition Tenacity (CN / Tex) Elongation at break (%) Orientation Index (CN / Tex)

one

- 23.5 123.4 18.9

2

70% PMMA 1 30% Smoke Black 15.1 183.2 6.9

3

85% PMMA 1 15% Ti02 16.6 171.0 8.1

4

70% PBT 1 30% Smoke Black 20.5 127.0 16.0

15 The results shown in Table 5 correspond to parameters of the load / elongation curve of 210 dtex POY polyester threads prepared under the same extrusion conditions, maintaining the same spinning speed of 3500 m / min. The results have been

20 deduced from the load / elongation curves of Figure 7 that correspond to a non-additive thread (RT20) (curves

l. 1-1. 3), and two-wire additivated with a quot; masterbatchquot; 70% PMMA 1 30% pigment. The pigment used in one case was Titanium Dioxide (Figure 7, curves 2.1-2.6), and

2 5 in the other case was Smoke Black (Figure 7, curves

3.1-3.3), and both additive threads contained 2.8% PMMA with respect to the fiber forming polymer. Table 5 confirms the decrease that occurs in fiber orientation (decrease in

5 I 100) when using PMMA as a support for a "masterbatch", both when the additive used is Smoke Black and when it comes to titanium dioxide. This demonstrates the effectiveness of the use of PMMA as a support for an additive, as it allows to increase the elongation to

10 the breakage of the POY polyester threads and, therefore, increase the spinning speed, which means an increase in the performance of this operation.

Table no.5

Test

Masterbatch composition Tenacity (CN / Tex) Medium Tenacity (CN / Tex) Elongation at break (%) Elongation at medium break (%) I1oo (CN / Tex) Medium 1 (CN / Tex)

1.1

- 24.4 23.6 126.3 125.5 19.0 18.5

1.2

22.9 123.9 18.3

1.3

23.5 126.2 18, 3

2.1

85% PMMA / 15% Ti02 (2, 8% PMMA + 0.5% Ti02) 16.8 16, 8 176.6 173.3 7.9 7.9

2.2

16, 4 168.4 8.0

2.3

17.7 179.7 7.9

2.4

17.0 171.0 8.0

2.5

16.8 171.4 7 '9

2.6

16.2 172.7 7.8

3.1

70% PMMA / 30% Smoke Black (2, 8% PMMA + 1.2% Smoke Black) 15.0 15.0 181.8 181.4 6.7 6.8

3.2

14.8 179.5 6.81

   3.3

15.2 183.1 6, 81

Example 5:

Comparative study between a POY thread from PES Standard

(RT20) and a thread added with a quot; masterbatchquot; with a

5

weight content of 85% PMMA 1 15% Ti02.

POY polyester threads of 2 90 dtex were prepared at

a spinning speed of 3500 m / min. additive with

different dosages of a quot; masterbatchquot; from

composition 85% PMMA 1 15% Ti02 •

10

Figure 8 contains the load-elongation curves of

the POY threads obtained, in which curves 1.1 and 1.2

correspond to the POY thread of PES Standard (RT20), the

curves 2.1 and 2.2 correspond to the 2% dosage

of the 'masterbatchquot; with a weight content of 85% PMMA

fifteen

1 15% Ti02, curves 3.1 and 3.2 correspond to the

3% dosage of the same quot; masterbatchquot ;, and

curves 4. 1 and 4. 2 correspond to the 4% dosage

from the same quot; masterbatchquot ;.

Table 6 shows the dosages applied

2O

to the polyester melts to be extruded and parameters of

these curves For their part, in Figure 9 they have

represented the elongation at break and the index of

orientation of these POY threads depending on the

Masterbatch dosage in molten polymer. In

25

she clearly shows that the lengthening to the

breakage increases and the orientation index decreases to

as the concentration of PMMA increases in the

   molten.

Table no.6

Test

Masterbatch dosage Tenacity (CN / Tex) Medium Tenacity (CN / Tex) Elongation at break (%} Elongation at medium break (%) I1oo (CN / Tex) Medium 1 (CN / Tex)

1.1

0% 22.9 22.7 133.1 132.0 16.7 16.9

1.2

22.5 130.8 17.0

2.1

2% 20.2 19.9 153.9 152.6 12.1 12.1

2.2

19.7 151.3 12.0

3.1

3% 19.0 18.7 167 '4 167 '4 10.3 10.3

3.2

18.3 167.3 10.4

4.1

4% 16.6 16.9 184.7 185.1 7.9 7.9

4.2

17.2 185.4 7.9

5 The prepared POY threads were textured by applying a stretch of 1.8, resulting in bent textured threads of a 340 dtex title. Tensile tests were performed to obtain the load-elongation curves of these textured threads, which are shown in the figure

10 10, and where curves 1-3 correspond to the additive threads with a dosage of 2% of the quot; masterbatchquot; mentioned above (with a weight content of 85% PMMA 1 15% Ti02), curves 4-6 correspond to the 3% dosage of said quot; masterbatchquot ;, and curves 7-9

15 correspond to a 4% dosage of this quot; masterbatchquot ;. From them, their toughness and elongation at break were calculated, which are contained in Table 7.

Table no.7

Masterbatch dosage

Medium Tenacity (CN / Tex) Elongation at medium break (%)

0%

-------- 12.3

2%

35.9 22.3

3%

33.7 28.6

4%

28.6 37.2

Figure 11 shows the elongation at breakage of

5 the textured threads depending on the dosing of the masterbatch in the melt, it being noted that it increases as it also increases.

As can be seen, the polyester thread without additive after texturing it, applying a stretched ratio of 10, has an elongation at break of 12.3%, while the thread containing 2.5% (3% of PMMA's masterbatchquot;) has an elongation at break of 28.6%, a value considered normal in a textured polyester thread. In order for the textured thread without additive to have an elongation at break of 28.6%, it would be necessary to texture it with a drawing ratio of 1.57, which would lead to a final title of 390 dtex. The possibility of applying a stretching ratio of 1.8 instead of 1.57 in the texture implies

20 a productivity increase of 15%. The calculations are obtained by applying the following expressions: DR x BREAK LENGTH = cte. % .6PROD. = (DR1-DR2) / DR2 X 100

25 Being: DR: drawing ratio

BREAK LENGTH = 100 + elongation at break% t:. = Increase in productivity

This is:

1.8 X 112.3 = DR2 X 128.6; DR2 l. 57 (1.8-1.57) / 1.57 X 100 = 15%

If the concentration of PMMA in the thread-forming polymer were 3.6% (4% of quot; masterbatchquot;), the elongation at break would be 37.2%, and to achieve it in a non-additive thread would be necessary

texture it

with a relationship from stretched from 1, 47,

resulting

a thread from 416 dtex In East case

(additivation

of the 3, 6% from PMMA) would result a increase from

the productivity of

22.3%

Example 6:

Comparison between two POY threads of polyester one of non-additive polymer (RT20 standard) and another of additive polymer with 4% of a "masterbatch"; with a weight content of 70% PBT 1 30% Smoke Black.

Two POY polyester threads of title 2 90 dtex were prepared with a spinning speed of 3500 m / min. One of them was made from a standard polymer (RT 2O) and the other from a polymer additive with 4% of a "masterbatchquot; 70% PBT 1 30% Smoke Black. Table 8 contains parameters of the load-elongation curve of these POY wires. As noted above (Table 4), the additivation with a quot; masterbatchquot; With a weight content of 70% PBT 1 30% Black Smoke leads to a certain elongation at breakage (greater deformability and stretchability) and also a decrease in the orientation index of POY polyester threads. It should be noted that in this

In this case, the content of Smoke Black in the thread forming polymer was 1.2%.

Table no.B

POY thread

Elongation at medium break (%) I1oo (CN / Tex)

PET RT20

Do not

134.2 17.0

additive

Additive

with 4% of

139.7 14.3

masterbatch

To know the extent to which these effects (increased elongation at breakage and decreased orientation index) are reflected in the thread properties

10 corresponding textures, the two POY threads were textured using a drawing ratio of 1.7, resulting in textured threads of title 360 dtex, whose toughness and elongation at break are indicated in Table 9. The results of this Table 9

15 show that the lower orientation index of the additive POY thread translates into a slightly greater elongation at the breakage of the corresponding textured thread.

Table no.9

POY thread precursor

Medium Tenacity (CN / Tex) Elongation at break (%)

PET RT20 Not additive

37.1 21.7

Additive with

4% of

341 4 23.6

   masterbatch

To differentiate the effects produced by the additivation with a quot; masterbatchquot; PMMA 1 carbon black

versus those that result from a "masterbatchquot; PBT 1 Smoke Black, we proceeded to the preparation of POY polyester threads starting from additive polymers with different concentrations of one "masterbatchquot; with a weight content of 70% PMMA 1 30% carbon black. POY threads were prepared with spinning speeds of 3000 and 3500 m / min., The molten polymer was added with 3% and 5% of this quot; masterbatchquot; and the POY threads obtained had a title of 2 90 dtex. Figure 12 shows the load / elongation curves of the POY threads resulting from spinning at a speed of 3500m / min. In it curves 1-3 correspond to a thread added with a quot; masterbatchquot; with a weight content of 70% PMMA 1 30% Smoke Black and dosed at 3% by weight in the thread-forming polymer, and curves 4-6 correspond to a yarn added with the same quot; masterbatchquot; but dosed at 5% in the wire forming polymer. The tensile parameters are summarized in Table 10.

From the values in this table, which also includes those obtained when spinning at 3000m / min, it follows that the additivation of the molten polymer with a "masterbatchquot; With a weight content of 70% PMMA 1 30% Black Smoke leads to high values of elongation at breakage and low values of the orientation index of the corresponding POY threads. The higher the percentage of additivation, the greater the elongation at break and the lower the index of orientation. On the other hand, an increase in the spinning speed, keeping the percentage of additivation constant, means, as

would fit

wait, a decrease of the elongation to the

break

Y a increase of the index of orientation.

Table

no.10

Additivation

Spinning speed (m / min.) Medium Tenacity (CN / Tex) Elongation at break (%) I1oo (CN / Tex)

Masterbatch (%)

PMMA (%) Smoke Black (%)

3000

18.6 198.9 8.1

3%

2.1% 0.9% 3500 19.9 159.3 11.5

3000

17.2 209.0 7.2

5%

3.5% 1.5% 3500 16.7 190.6 8.0

5 Taking into account that with a 4% additivation with a quot; masterbatchquot; 70% PBT 1 30% carbon black, spinning at 3500 m / min., An elongation at break of 139.7% and an orientation index of 14.3 CN / tex, it is evident that the use of PMMA as support of

10 carbon black leads to much better results than when PBT is used as support (see Table 4).

Example 7: Comparative study of the influence of

15 dosage with different percentages of one quot; masterbatchquot; with a weight content of 70% PMMA 1 30% Smoke Black.

Five POY polyester threads of 290 dtex have been prepared with a spinning speed of 3500 m / min. The 20 castings extruded to manufacture these threads were characterized because some of them had not been additive, another had been with 4% of a "masterbatchquot; with a weight content of 70% PBT 1 30% Smoke Black, and the other three were added with 3, 25, 4 and 5% respectively, of a "masterbatchquot; with a

70% PMMA 1 30% Smoke Black weight content. Table 11 contains the most important tensile parameters deduced from the corresponding load-elongation curves (not shown). From the values in this table, it is confirmed that the presence or additivation with carbon black with PBT as a carrier produces certain favorable effects on elongation at break (increasing it) and on the orientation index (decreasing it). Based on what matters most about this example, Table 11 also shows that the higher the concentration of "masterbatchquot"; in the melt, the elongation at breakage is greater and the index of orientation of the corresponding POY threads is lower. It can also be added that for the same concentration

15 carbon black (1.2%) shows a greater increase in elongation and a greater decrease in orientation when the presence of carbon black coincides with that of PMMA (2.8).

Table no.11

Test

Additivation Medium Tenacity (CN / Tex) Elongation at break (%) IlOO (CN / Tex)

Masterbatch (%)

PMMA (%) Smoke Black (%)

one

- - - 23.2 134.2 17.0

2

- - 1.2% 20.5 139.7 14.3

3

3% 2.1% o '9% 18 '9 152.6 11.7

4

4% 2.8% 1.2% 18.5 167 '3 10.2

5

5% 3.5% 1.5% 16.5 186.1 8 '1

With the POY polyester yarn added with a quot; masterbatchquot; of 5% a textured thread was prepared by applying a drawing ratio of 1.95, so that a thread with a toughness of 30 CN / tex and an elongation at break of 25% resulted.

Taking these values into account, the breaking length that will correspond to a POY thread added with 5% of quot; masterbatchquot; applying a stretch ratio of l.8 will be:

(125x1.95) / 1.8 = 135%

If it is taken into account that a POY thread of PES Standard spun at 3500 m / min and textured after applying a drawing ratio of 1, 8 has an elongation at break of 12%, so that the PES Standard has a breaking length of 135% the stretching ratio should be:

(112x1.8) / 135 = 1.49

So the increase in productivity that would result from the additivation with 5% of the "masterbatchquot; 70% PMMA 1 30% carbon black would be:

(1.80-1.49) x 100 / 1.49 = 20.8%

As a conclusion after the exposure of the tests carried out, it can be noted that the application of a "masterbatchquot; With a weight content of PMMA / Ti02 (Ti02 matt pigment) allows a yield increase of 22.3%, and 20.8% when applying a "masterbatchquot"; PMMA / carbon black.

Described sufficiently the present invention in correspondence with the attached figures, it is easy to understand that any modifications of detail that are deemed convenient may be introduced therein, as long as the essence of the invention is not altered, which is summarized in the following claims.

Claims (1)

la.-Concentrated polymer composition (`` masterbatchquot;) that is incorporated during the extrusion process to the melts of polyester polymers forming fibers and filaments characterized in that it comprises: a carrier polymer ("carrier") wherein said carrier polymer comprises at least one polymer of the methacrylate family with a molecular weight between 10,000 and 500,000 g / mol, said carrier polymer being contained in an amount of between 30 % and 99% by weight in the polymer composition; Y at least one additive and / or a pigment, being contained in an amount between 1% and 70% by weight of said polymer composition. 2a.-Concentrated polymer composition according to claim 1, characterized in that the support polymer ("carrier") is polymethylmethacrylate (PMMA).

Composition

polymeric concentrated according the

claims

1 a or 2 a, characterized why he

pigment

be choose from between a  pigment organic, a

inorganic pigment,

or their mixtures

4a.-Concentrated polymer composition according to claim 3, characterized in that the pigment chosen is Smoke Black. 5a.- Concentrated polymer composition according to claim 3, characterized in that the pigment chosen is Titanium Dioxide (Ti02). 6a.-Concentrated polymer composition according to claims la or 2a, characterized in that additionally the support polymer contains, in addition to the polymethylmethacrylate, one or a combination of at least two of the following polymers: polybutyleneterephthalate (PBT), polyethylene terephthalate (PET), polymethyl terephthalate (PTT), or polylactic acid (PLA). 7a.-Concentrated polymer composition according to claims la or 2a characterized in that the additive is chosen within the group formed by

lubricants,

antistatic, plasticizers,

stabilizers,

antioxidants, compatibilizers and

flame retardants as well

how their mixtures

sa.-Concentrated polymer composition according to any of claims 1a_4a, characterized because it comprises between 60-80% by weight of polymethylmethacrylate (PMMA) as a support polymer and between 20-40% by weight of carbon black as pigment. ga__ Concentrated polymer composition according to any one of claims 1 to -4 a, characterized

why

understands between a 50-95% in weight from

polymethylmethacrylate

(PMMA) how polymer support Y

between

a 5-50% in weight from Dioxide from Titanium (Ti02) how

   pigment.

Concentrated polymeric composition according to any of claims 1a_ga, characterized in that said composition additionally comprises dispersing agents. lla.-Method of manufacturing a concentrated polymer composition ("masterbatchquot;), defined according to any of claims la-loa, characterized in that it comprises an extrusion phase and optionally a pre-mixing pre-phase. 12a.-Manufacturing process according to the claim, characterized in that the extrusion phase comprises obtaining a good dispersion (dispersive mixture) and homogenization (distributive mixture) of the components of the `` masterbatchquot ;, by means of an extruder, preferably of the bi-spindle type, which transfer a large amount of mechanical energy to the material, and where high pigment contents are dispersed and / or additives, and where the spindles are formed by different assembled elements that, depending on their geometry and position, distribute, disperse, or transport the material.
13a.-Manufacturing process according to claim 11, characterized in that the optional pre-mixing phase comprises the pre-dispersion of the pigments and / or additives by using one or more dispersing agents, compatible with the polymer of the base and with the polymer component of the fiber to be manufactured, where the agglomerates are broken down by effort mechanic provided by the turbo-mixer blades and the subsequent imbibition or impregnation of the pigment particles. 14a.-Use of a concentrated polymer composition, defined according to any of claims la-lOa, characterized in that said composition is added to the melts of polyester polymers, where the polyester is selected from the group consisting of polyethylene terephthalate (PET), polybutyleneterephthalate (PBT), polytrimethylene terephthalate (PTT) or acid

polylactic

(PLA), Y why bliss polymeric composition

concentrated

be add to saying molten in a

proportion

such that he polymethylmethacrylate (PMMA)

It has a final concentration of up to 10% by weight in said melt. 15a.-Use of the concentrated polymer composition (quot; masterbatchquot;), according to claim 14 a, characterized in that the addition of said concentrated polymer composition allows a 40% +/- 10% increase in elongation at breakage in spinning, and a decrease in the index of orientation I 100 of 10 cN / tex +/- 5 cN / tex when spinning at speeds between 2000-4000 m / min., increasing the collection speed and spinning process performance by more than 20%. 16a.-Use of a concentrated polymer composition, defined according to any of claims 1a to 10a, for the production of pre-oriented threads that are
they spin at speeds of between 500 and 4500 m / min. 17a.-Use of a concentrated polymeric composition according to claim 16a, for the production of pre-oriented threads that are spun at speeds of between 2000 and 4000 m / min. 18a.-Use of a concentrated polymer composition according to claim ga, characterized in that said polymer composition is added in an amount between

he

2% Y  he 8% in weight to the molten of the polymer from

polyester

trainer from fibers Y filam entos, Y he

polymethylmethacrylate

is content in a quantity

between 1.4% and 5.6% by weight in said melt. 19a.-Use of a concentrated polymer composition according to claim 18a, characterized in that said composition decreases the orientation index of pre-oriented polyester yarns to values between 11.7 (CN / tex) and 8.1 (CN / tex) when they are spun at speeds between 2000 and 4000 m / min. 20a.- Use of a concentrated polymer composition according to claim ga, characterized in that said polymer composition is added to the melt of the polyester polymer of fibers and filaments in an amount between 2% and 8% by weight, and the polymethylmethacrylate it is contained in an amount between 1.7% and 6.8% by weight in said melt.
21st -Use of a concentrated polymer composition according to claim 20a, characterized in that said composition decreases the orientation index of pre-oriented polyester yarns to values between 12. 1 (CN / tex) and 7.9 (CN / tex) when they are spun at speeds between 2000 and 4000 m / min. 22a.-Use of a concentrated polymer composition, 5 defined according to any of claims 1a-10, characterized in that said composition is added as a solid pellet by means of a gravimetric system (with or without a mixer) in the melt extrusion zone of the fiber forming polymer. 23a.- Use of a concentrated polymer composition, defined according to any one of claims la-lOa, characterized in that said composition is added in the molten state by means of a lateral extruder to the area
15 melt extrusion of the fiber forming polymer.